四氢双环戊二烯异构化过程的溶剂效应

Solvent Effect in Isomerization of Tetrahydrodicyclopentadiene

采用无水AlCl3为催化剂,考察了使用不同溶剂对桥式四氢双环戊二烯(endo-THDCPD)异构化为挂式四氢双环戊二烯(exo-THDCPD)过程中反应速率、反应转化率、收率、选择性及杂质生成量的影响。采用气相色谱对反应原料、产物及杂质进行定量分析。结果表明溶剂的使用对于异构化反应有显著的影响:甲苯作溶剂时对反应有很大的抑制作用,而1,2-二氯乙烷作溶剂时,则有明显改善,在催化剂浓度3%(wt)、最佳反应温度60°C条件下,反应结果:转化率97.73%、收率97.66%、选择性99.93%。同无溶剂反应时相比,最佳反应温度降低、产物中金刚烷生成量减少同时无焦油产生。实验中以原料endo-THDCPD为对象考察1,2-二氯乙烷作溶剂时的反应动力学,得到了动力学方程。

Exo-tetrahydrodicyclopentadiene(exo-THDCPD), the isomer of endo-tetrahydrodicyclopentadiene (endo-THDCPD), can be used as an excellent liquid fuel with high density, high heating value and low viscosity at low temperature. For the isomerization of endo-THDCPD to exo-THDCPD, AlCl3 was used as catalyst with different solvents. Effect of the solvents on reaction rate, conversion, yield, selectivity and by-product was investigated. The results show that different solvents have different effect on the isomerization. Reaction conversion and yield decrease greatly with toluene as solvent. Compared with the isomerization without solvent, using 1,2-dichloroethane as solvent has the best effect on the isomerization with the optimal reaction condition: temperature 60°C, catalyst 3%(wt), during which, less adamantane and no tar are founded in the product. The reaction results are: conversion 97.73%, yield 97.66% and selectivity 99.93%. Kinetic equation of endo-THDCPD isomerization was obtained.